DE2013791A1 - Yellow basic hydrazone dyes for polyacry-lonitrile etc - Google Patents

Abstract

Basic yellos dyes of the hydrazone series for dyeing/Printing leather, mordanted cellulose acetate, jute, sisal, in flexographic printing, printing and writing inks, and for dyeing/printing polyacrylonitrile and acrylonitrile copolymer and acid-modified aromatic polyesters, esp. on polyacrylonitrile material, have the formula: (where R is aromatic carbocylic; R1 is H or alkyl; R2 is H, alkyl, alkoxy, amino opt. substd. by alkyl groups or by an acyl, sulphonyl or carbamoyl group; R3 is H, alkyl or alkoxy; R4 is alkyl; R5 is nitrile or opt. substd. carboxamide; R6 is H, alkyl, aralkyl or cycloalkyl; X is the radical of an anion; the aliphatic, cycloaliphatic and aromatic radicals R-R6 are unsubstd. or may be substd. by non-ionic substituents having a Hammett para sigma-constant of less than 0.7).

Description

wherein R for an aromatic-carbocyclic radical, R ^ for hydrogen or an alkyl radical, R ₂ for hydrogen, an alkyl, alkoxy or an amino group R, optionally substituted by alkyl groups or by an acyl, sulfonyl or carbamoyl radical, for hydrogen , an alkyl or alkoxy radical, R. for an alkyl radical, R ^ for the cyano or an optionally substituted carbonamide group and Rg for hydrogen or an alkyl, aralkyl or cycloalkyl group and X for the radical of an anion and in which the aliphatic, cycloaliphatic and aromatic radicals R, R ^,

Rc and

other non-ionic sub-

substituents with a Hammett constant <y para

Le A12887

may be less than 0.7,

Process for their production and their use for dyeing and printing.

(For Hammett constants C ~ para see HA Staab, Introduction to Theoretical Organic Chemistry, 1959, Weinheim, especially page 584). Al3 such non-ionic

Substituents come into consideration, for example: lower alkyl and alkoxy radicals with 1-4 carbon atoms such as methyl, Ethyl, n-propyl, iso-propyl, η-butyl, iso-butyl, methoxy, Ethoxy, n-propoxy, iso-propoxy, n-butoxy and iso-butoxy, aralkyl, such as benzyl, ar-alkoxy, such as benzyloxy, aryl, such as Phenyl and phenyl radicals substituted by non-ionic radicals, z. B. chlorophenyl, methylphenyl, aryloxy groups such as phenoxy, halogen substituents, especially Cl and Br, carboxylic acid ester groups, optionally N-substituted carbonamide groups, lower alkyl groups having 1-4 carbon atoms, optionally substituted, being preferred as substituents Amino groups, acyloxy groups such as acetoxy, Acylamino groups such as acetylamino, methylsulfonylamino and AcWl residues, like the acetyl residue.

A group of preferred dyes corresponds to the formula

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where R ₁ ¹ for hydrogen or methyl, R ₂ 'for hydrogen, methyl, methoxy, ethoxy, acetylamino, benzoylamino or ur.eido, R · *''"for hydrogen or methyl, R · for methyl or .ethyl, R ₅ 'is cyano, carboxamido or N-Methylcarbonamido, Rg' is hydrogen, methyl, ethyl or n-Eutyl, R ₇ ¹ is hydrogen, methyl, M _e thoxy, ethoxy or phenoxy, R q ¹ represents hydrogen, methyl, methoxy, ethoxy or benzyl, Rg 'for hydrogen, chlorine, methyl, methoxy, ethoxy, phenoxy, acetylamino, benzoylamino, N, N-diethylsulfonylamino, cyclohexyl, benzyl, benzyloxy, optionally phenylazo or 6-methylsubstituted by methyl and methoxy -benzthiazolyl-2- ,, R ^ ₀ * stand for hydrogen, methyl, methoxy or chlorine, and in which the phenyl nucleus can be fused with a tetramethylene bridge to form a 5, 6, 7, 8-tetrahydronaphthylamine-1 radical and X is "an anion".

Another group of particularly valuable dyes corresponds the general formula

f4 " ■ ■. .- ■ - ■: '·: -.-H-. -Rl -I R ''
² ^ CN I. - --- = R ₃ - ^R 4 ^r :

(III)

wherein R ¹ 'is a benzene radicalyR-i ¹ ' is hydrogen or an alkyl radical having 1-4 carbon atoms, R ₂ ¹ ! and-.Hj ¹¹ . Hydrogen, an alkyl or

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1 0984? / 1 / i 8 0

Alkoxy radical with 1-4 carbon atoms and R. '' an alkyl radical with 1-4 carbon atoms and X an anion and in which R ¹ can carry substituents with a Hammett constant r * para less than 0.3.

The new dyes of the general formula I, in which R, represents hydrogen, are obtained by adding amines to the formula

where R is an aromatic-carbocyclic radical £,

diazotized and with compounds of the general formula

wherein

R ₁ for hydrogen or an alkyl radical, R ₂ for hydrogen, an alkyl, alkoxy or an amino group optionally substituted by alkyl groups or by an acyl, sulfonyl or carbamoyl radical, R, for hydrogen, an alkyl or alkoxy radical, R. for an alkyl radical, R ₅ for the cyano or an optionally substituted carbonamide group and in which the aliphatic, cycloaliphatic and aromatic radicals R, R ₁ , R _2,. R ,, R. and Rc further non-ionic substituents with a Hammett constant σ- para less than 0.7

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can have
clutch.

Another method of preparing the dyes of the general Formula I in which Rg is hydrogen " in that one aromatic-carbocyclic amino compounds of the formula. .

vorin R represents an aromatic-carbocyclic radical,
with compounds of the general formula

^E l - "Ν I.
^E 4 Ε,

C - GH ₂

X "

(IV a)

in which

R ₁ for hydrogen or an alkyl radical, R ₂ for hydrogen, an alkyl, alkoxy or an amino group optionally substituted by alkyl groups or by an acyl, sulfonyl or carbamoyl radical, R for hydrogen, an alkyl or alkoxy radical, R ^ for an alkyl radical, H ^ for the gyan or an optionally substituted carbonamide group and X for the radical of an anion and in which the aliphatic, cycloaliphatic and aromatic

and B ₅ more non-

between radicals R, R ₁ , R ₂ , R «j _t
can have ionic substituents with a Hammett constant <y para less than 0.7,

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clutch.

Dyes of the general formula I ₁ in which Rg denotes alkyl, cycloalkyl or aralkyl are obtained if, for example, basic dyes accessible by one of the processes described above are incorporated into the azo base of the formula in a manner known per se with the aid of acid-binding agents

f I ⁴ ? 5 ^R 2 _X ^R 3 ^ I. ^E 4 3 · ^R 4 wori η R, ^ l ' ^R 2' ^

and R ^ have the meaning given above,

and converts this in the presence or absence of a Solvent or diluent, if appropriate at elevated temperature with a quaternizing agent, into the ammonium compound convicted.

The following aroaatic, for example, are suitable as starting material for the preparation of the dyes according to the invention Amines HpN-R:

Aminobenzene, 4-chloro-1-aminobenzene, 2-, 3- or 4-methyl-laminobenzene, 2-, 3- or 4-methoxy-l-aminobenzene, 2-, 3- or 4-ethoxy-l-aminobenzene, l-amino-2, 4-dimethylbenzene, 1-amino-2,5-dimethylbenzene, l-amino-3,4-dimethylbenzene, l-amino-2,4-dimethoxybenzene, l-amino-2,5-dimethoxybenzene, 2-aminodiphenyl ether, 4-aminodiphenyl ether, l-amino-4-acetylaminobenzene,

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l-Amino-4-benzoylaminobenzene, l-Amino-2-methoxy-5-chloro "benzene, l-Amino - ^ - methoxy ^ -sulphonic acid diethylamide, l-Amino-4-cyclohexylbenzene, l-Amino-4-benzylbenzene , l-amino-3-benzylbenzene, l-amino-4-benzyloxybenzene, 2- (4 ^l -amino-phenyl) -6-methyl-benzothiazole, 4-amino-azobenzene, 4-amino-4'-methoxyazobenzene, 4 -Amino-4 ^l -methylazobenzene, 5, 6, 7, 8-tetrahydro-lnaphthylamine.

The coupling components IV are particularly suitable following connections:

1,3-dimethyl-2-cyanomethylene benzimidazoline, 1,3 »5-trimethyl-2-cyanomethylene benzimidazoline, 1, 3, 4, 5, 6-pentamethyl-2-cyanomethylene benzimidazoline, 1,3-dimethyl-5-methoxy-2- cyanmethylene benzimidazoline, l, 3-dimethyl-5-ethoxy-2-cyanmethylene benzimidazoline, l, 3-J-dimethyl-5-acetylamino-2-cyanomethylene benzimidazoline, l ^ -dimethyl-S-benzoylainino - ^ - cyanine ethylene benzimidazoline-5, l, -ureido-2-cyanomethylene benzimidazoline, l _t 3-diethyl-2-cyanπlethylene benzimidazoline, 1,3-methyl-5-methyl-2-cyanomethylene benzimidazoline, 1,3-diethyl-5-ethoxy-2-cyanomethylene benzimidazoline, 1,3- Dimethylbenzimidazolinylidene-2-acetic acid amide and 1,3-dimethylbenzimidazolinylidene-2-acetic acid methylamide.

The preparation of the coupling components is carried out in a known manner by alkylation of the 2-Cyanmethylbenzimidazols or the 2-Carbonamidomethylbenzimidazols and its substitution products in aqueous or organic M _e dium with addition of an acid-binding agent. The 5-amino-1,3-dimethyl-2-cyanomethylene benzimidazoline derivatives are obtained by nitrating 1,3-dialkyl-2-cyanomethylene benzimidazoline and subsequent reduction or catalytic hydrogenation; the further

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Implementation of the amino compound with acylating agents to the The compounds on which formula (IV) are based are carried out in the customary manner.

The coupling is carried out in the usual way by adding the diazonium salt solution for the hydrochloric acid solution of the benzimidazoline compound at 0-10 ° and the addition of acid-binding agents such as sodium acetate executed.

The quaternizing agents include dimethyl sulfate, diethyl sulfate, methyl iodide, methyl 4-toluenesulfonate, Ethyl 4-toluenesulfonate and butyl 4-toluenesulfonate into consideration.

Suitable solvents and diluents are, for example Acetone, ligroin, gasoline, benzene, chlorobenzene, toluene, xylene and chloroform.

The anionic groups X "can be both inorganic and organic, I _o nen be, for example, are: Cl", Br ", J", CH ₅ SO ₄ ", C ₂ H ₅ SO _4," p.Toluolsulfonat, HSO. ", Benzenesulfonate, p-chlorobenzenesulfonate, phosphate, acetate, formate, propionate, oxalate, lactate, maleate, crotonate, tartrate, citrate, NO, ~, perchlorate, ZnCl,". The nature of the anionic radicals is irrelevant for the properties of the dyes, provided that they are largely colorless radicals which do not adversely affect the solubility of the dyes.

The products according to the invention are valuable dyes which are used for dyeing and printing leather materials Cotton, cellulose acetate and for dyeing lignin-containing

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Fibers like coconut, jute and sisal can be used. she are also suitable for the production of writing fluids, stamp inks, ballpoint pen pastes and can also be used in the Use rubber pressure.

For dyeing and printing with the basic dyes of the above general formula, flakes, fibers, threads, tapes, woven or knitted fabrics made of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole, are particularly suitable. Vinyl alcohol, acrylic and methacrylic acid esters and amides, as. Dicyanäthylen, whereby some of the dyes are characterized by high drawing speed, or for dyeing flakes, fibers, threads, tapes, woven or knitted fabrics made from acid-modified aromatic polyesters, as well as acidic for dyeing modified polyamide fibers. Acid-modified aromatic polyesters include polycondensates of sulfoterephthalic and ethylene glycol, ie sulfonic Polyäthylenglykolterephthalaten (type DACROU 64 of EI Du Pont de _Ne Mours and Company), as they are in the "Belgian Patent 549,179 and US Patent No. 2,893,816 describes . ·.

The dyeing can be carried out from a weakly acidic liquor, in which case the dye bath is expediently entered at 40-60 ° α: and then dyed at boiling temperature. You can also dye under pressure at temperatures above 100 ° G. Furthermore, the dyes can be added to the spinning solutions for the production of polyaerylnitrilhalti ger fibers or also to the. Apply undrawn fiber. . ■ _. , " ..., - · ..-. ■■■" .. ■ ■■■ , .- ■■; · ■■

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The dyeings available according to the invention on polyacrylonitrile-containing Material are characterized by very good light, wet, rubbing and sublimation fastness. The dyes form with anionic precipitants, such as clay, tannin, Phosphorwolf ram (molybdenum) acids, lightfast pigments, which are beneficial can be used in paper printing.

The dyes can be used either individually or in mixtures. Mixtures show in many cases Coloring on polyacrylonitrile materials has a higher color strength.

Compared with the coupling products of diazotized aromatic amines on 1, 3, 3-trimethyl-2-methyleneindoline (reports from Deutsche Chemischen Gesellschaft 57 (1924) p. 144 ff.) The colorations of the dyes according to the invention are distinguished on polyacrylonitrile due to a significantly improved lightfastness.

Example 1t

IC), 7 parts of 1-amino-4-methylbenzene are, after dissolving in 150 parts by volume of 6% aqueous hydrochloric acid, cooled to 0-5 ° C. and diazotized with 7.3 parts of sodium nitrite in 20 parts of water. After stirring for about 30 minutes, the excess nitrous acid is destroyed by sulfamic acid and the diazo solution is poured into the clear, cooled to 10 ° C solution of 18.5 parts of 1,3-dimethyl-2-cyanomethylene-benzimidazoline in 150 parts by volume of 5% aqueous hydrochloric acid Stir filtered in. After stirring for 30 minutes, the mixture is blunted with 300 parts by volume of 20% aqueous sodium acetate solution and the yellow precipitate which separates out is stirred for a few hours at room temperature. After filtration with suction and washing on the filter with 500 parts by volume of 5 $ aqueous K _o chsalz-

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solution you get a yellow coupling produtt. 10 parts of this Moist product are boiled in 500 parts by volume of water and treated with 30 parts by volume of 10 ^ iger aqueous hydrochloric acid in the heat added, whereby a clear yellow solution is formed. After filtering and cooling, the dye thus represented is salted the formula

ι

with 32 parts of sodium chloride, which after suction, washing with dilute aqueous saline solution and drying to 6.2 Parts accumulate and melts between 210-212 ° C with decomposition. This dye stains polyacrylonitrile, its Copolymers with vinyl compounds, acid modified polyesters and polyamides in a clear greenish yellow Shade on. The dyeings are particularly notable for their excellent lightfastness.

In accordance with this method of operation, starting from the corresponding starting components, additional components listed below are obtained valuable dyes:

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dye

Color on polyacrylonitrile

CH

C-C =

CH, - N -I / "^

CH Cl "greenish yellow

CH,

f ³ .N CN

; c -c = ν -

CH,

OCH, Cl "yellow

? ^H 3

C -

OCH,

CN H C = N-N-

CH, Cl yellow

CH, I J

CN H

C-C = N-N- / ~~ V NH - C

CB, Cl Reddish.

yellow

Le-A '12887

? ^B 3

SN '■' GH,

dye

CN H

C-C = N-N

Color on polyacrylonitrile

Greenish yellow

CH,

I J

CN H -C = N-N

Cl

CH ₃ Ci "greenish tinge" yellow

CH ₃ • Ν

^% C -

CN H

C = N-N

CH, Cl "reddish yellow

QCH,

CN

: c - c = ν -

Yellow-red Öjrrang,

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Λ1

CH,

NN

dye

CN H

C = N-N

OCH

-CH,

Color on polyacrylonitrile

Cl

Reddish yellow

? ^H 3

CN

cc = NNf Vn = N- / ⁷ ^

, ___ CH ₃ Cl "reddish yellow

CH

[^ JLn

CN C-C = N-

CH, he

Greenish yellow

OH-

I J

CH,

CN H

C = NN -ζ ~ \ ~

Cl "greenish yellow

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Ear stuff

CH

.N

CN C-C =

CH he

Color shade on polyacrylonitrile

yellow

IH ₃ C

-C = N-

OCPL

^cl ~ yellow

CH

-N.

CN

G-C = N- N -

Cl "greenish yellow

do

G -

CN H

C = N - N.

CH,

XV ^ NH - CO - CH,

Cl "

QN; H

Cl

σί

Dye CH,

JN

OCH

CN G-C = N

CH,

Color on polyacrylonitrile

Cl "" Greenish yellow

? ^H 3

N ^ CH,

OCH

GN

'C -

Cl "

Greenish yellow

.N '' CH-

CN H _ Ji

c -c -n- \ - (Jy (^,

CH,

Cl "

Reddish yellow

"N,

C -

CN H C = N-N N = N-

CH,

Cl

Reddish yellow

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U80

4?

dye

Color on polyacrylonitrile

. c -

CN H

C = N

_ N - / j) - (h

CH

Cl "yellow

, N

CH-

CN
"CC = N-

Cl "yellow

CN H

-C = N-N

CH ₂ -

CH-

Cl "

Greenish yellow

CH,
» J CN
t N - H + Cl " ^N x ) - C = N - <f V Greenish yellow 1"
I. CH, -CH ₃

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dye G - H - H y ^H 3
J-Q Hue on
Polyacrylonitrile +
Cl "yellow / N
CO +
Cl "yellow - CH ₅ C - N - H H ₅ C ₂ O -, CH _x OCH CH ₅ CN
I.
- C = CN
ι
- C =

H ₅ C ₂ O

CH,

CH

CN

-C = N-

OCH,

Cl

Cl "

yellow

H ₅ O ₂ O

JJ

• N CH-

CN C-C = N-

OCH

Yellow

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dye

2G13791

Color on polyacrylonitrile

H ₅ C ₂ O

C -

CH

OCH.
H \. '

(>^so;

- N.

- C ₂ H ₅

Cl yellow

Il

C -

^{1) 11} OC

CH.

f -N

CN H _r __

C = NN- / ^V

CH,

Cl "yellow

OH -G = N - H I. I. \ CONH ₀ N N * ^ CH ₅

CH.

Cl "

Greenish yellow

CH- - C = H- H r- ⁵ I. - N f - V ^ i L Ji-N 4 lc

OCH

GH

'JIi

. or

Le, A 128 & 7,

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A2 / i 48

2fr

pH *,

CN

CH ₇

• N
CH

C -

"/ ^CH 3

Cl "

Greenish yellow

CH,

CN

C -

^CH

OCH-

CH, ^CH 3 Cl "yellow

7 3

OH,

CN

C-C =

N -

CH.

Greenish

yellow

CH
CH ₃ f

CN

C-C = N

21 "yellow

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example 2%

39.7 parts of the moist coupling product prepared according to the procedure for Example 1 are 800 parts by volume
Slurried water at room temperature and made alkaline with 10 parts by volume of 10 subsequent soda solution to p "= 11. The mixture is then stirred for 3 hours at 40 ° C. and for about 20 hours at room temperature, filtered off with suction and washed neutral with water. The crude product precipitates after recrystallization
Dimethylformamide and drying to 18.3 parts pure from the melting point 256-260 ° C.

This substance is heated in 100 parts by volume of toluene to 50 ° C., 9 »1 parts of dimethyl sulfate are added dropwise and heated for 2 hours on a water bath. After further addition of 4.6 parts of dimethyl sulfate and heating for 3 hours, a separates out
crystalline compound, which after drying to 26.3 parts
accrues. After dissolving in 1500 parts by volume of hot water,
Filtration and cooling of the solution as well as salting out with 70
Parts of common salt result in 13.6 parts of dry dye
of the formula - - ■.

CH.

C-

CN CH, C = N- N- '

CH

which melts between 223-225 C.

This dye dyes polyacrylonitrile and the above-mentioned materials in a greenish yellow shade with good generality Authenticity level.

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Further dyes produced according to this example are listed in the following table:

dye

CH ₃

CN

C = N CH ₅

Color on polyacrylonitrile

.CIL

Cl "

Greenish yellow

CH,

f ° , N CN

; c _c =

CH,

CH

OCH, Cl "

Greenish yellow

CH

cn

CH,

C-C = N-N-

NH-C- CH,

Reddish yellow

Cl "

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dye

Color on polyacrylonitrile

? ^H 3

CN t

CH,

Red deep yellow

Cl "

CH,

I J

.N

-N ^
CH,

CN

fs

C-C = N-N.

^CH -:

Cl '

Greenish yellow

CH,

CH,

CN

CH,

-C-C = N - N -

OCH,

Greenish
yellow

CH

-C = N-N- / Vy-NH-CO-CH

Cl '

Reddish yellow

CH,

CN

CH,

C-C = N-N- ^

.CH,

Cl

yellow

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dye

3!

Color on polyacrylonitrile

H, C

? ^H 3

CH

CN C

C-C = N-N-

SO ₂ -N
^ά \ C

2 ^H 5

Cl "yellow

? ^H 3

CN

-C = N- N "- /" Λ N = N -f \

W W

CH,

OH,

, N

Cl "golden yellow

.C -

CN C = N

CH

CH,

Cl "

yellow

CH 7 3

, N

■ N
CH.

CN C-C = N-

OH ₂ -Q

Cl "
yellow

²⁰ O CH,
I J 1 CN
C = N- CH ₃
N - <f ~ V GH, +
Cl " - I.
CH, V = - '' Greenish
yellow Le A 12887 - 24th
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dye

Polyacrylonitrile

CH

CH,

^CN

-C = N-N-

OCH.

CH

Greenish yellow

Cl "

H _c C _o 0

CH,

CH,

C-C = N-N-

CH

Greenish yellow

Cl

CH,

• Ν

CN

C-C

νΛ-fXf ι

CH,

Cl

orange

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Example 3t

PolyacrylnitriIfasem at 40 ° C in a liquor ratio 1: 40 is introduced into an aqueous bath containing, per liter 0.7T> 30 g follow acetic acid, 0.38 g of sodium acetate and 0.3 g of the dye of the formula

CH

C.

CN H -C = N-N

CH,

Cl "

contains. The mixture is heated to the boil within 20-30 minutes and the bath is kept at this temperature for 30-60 minutes. Afterward the polyacrylonitrile fibers are rinsed and dried. They are in a greenish yellow with a very good fastness properties dyed.

Example 4:

Acid modified polyglycol terephthalate fibers are introduced into an aqueous bath at 20 C in a liquor ratio of 1:40, 6 - 10 g of sodium sulfate, 0.5 - Ig per liter Oleyl polyglycol ether (50 mol ethylene oxide), 0-15 g dimethylbenzyl-dodecylammonium chloride and 0.3 g of the dye

CN

= N-N

CH,

Cl "

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contains and was adjusted with acetic acid to p _H .4 up. 5 The mixture is heated to 120 ° C. in the course of 30 minutes and the bath is kept at this temperature for 60 minutes. The fibers are then rinsed and dried. A greenish yellow dyeing with very good fastness properties is obtained

Example 5:

A polyacrylonitrile fabric is printed with a printing paste, which were produced in the following manner 30 parts by weight of the dye of the formula

CN C - C = N

-N

CH

Cl "

50 parts by weight of thiodiethylene glycol, 30 parts by weight of cyclohexanol and 30 parts by weight of 30% acetic acid are poured with 330 parts by weight of hot water and the resulting solution is added to 500 parts by weight of crystal gum (gum arabic as thickener). Finally, 30 parts by weight of zinc nitrate solution are added. The pressure obtained is dried, steamed for 30 minutes and then rinsed. A greenish yellow print with very good fastness properties is obtained. ·

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.109842 / 1480

Claims (9)

Claims 1- Basic dyes of the general formula C-C = N-N-R wherein R stands for an aromatic-carbocyclic radical, R ₁ for hydrogen or an alkyl radical, R ₂ for hydrogen, an alkyl, alkoxy or an amino group optionally substituted by alkyl groups or by an acyl, sulfonyl or carbamoyl radical, R for hydrogen , an alkyl or alkoxy radical, R. for an alkyl radical, R_ for the cyano or an optionally substituted carbonamide group, R ₆ for hydrogen or an alkyl, aralkyl or cycloalkyl group and X for an anion and in which the aliphatic, cycloaliphatic and aromatic radicals R, R _n , R _n , R ,, R., R ,. J- £ 5 4 5 and Rg can have further non-ionic substituents with a Hammett constant <r para less than 0.7. Le A12887 - 28 - 109842/1480 2. Basic dyes of the general formula C-C = N-- X " where R- ' for hydrogen or methyl, R 'for (II) Hydrogen, methyl, methoxy, ethoxy, acetylamino, behzoylamino or ureido, R, ¹ for hydrogen or methyl, R for methyl or ethyl, R for cyano, carbonamido or N-methylcarbonamido, R ^ for hydrogen, methyl, ethyl or η-butyl, R ₇ 'is hydrogen, M _e methyl, methoxy, ethoxy or phenoxy, Rg' is hydrogen, methyl, methoxy, ethoxy, or benzyl, R _g · represents hydrogen, chlorine, methyl, methoxy, ethoxy, Phenoxy, acetylamino, benzoylamino, N, N-diethyl-sulfonylamino, cyclohexyl, benzyl, benzyloxy, optionally phenylazo or 6-methyl-benzthiazolyl-2-, R _{10 represent} hydrogen, methyl, methoxy or chlorine, and in which the phenyl nucleus can be fused with a tetramethylene bridge to form a 5, 6, 7, 8-tetrahydronaphthylamine-1 radical, and X ″ stands for an anion. Le A12887 109842/1480 3. Basic dyes of the general formula N. .N CN H C = N-N-R " where R '' is a benzene radical, R ₁ ¹ 'is hydrogen or an alkyl radical having 1-4 carbon atoms, R _{2 is} ¹¹ and R, ^{11 is} hydrogen, an alkyl or an alkoxy radical having 1-4 carbon atoms and R. 4 carbon atoms and X is an anion and in which R ¹ · can carry substituents with a Hammett constant <r para less than 0.3. 4. Process for the preparation of dyes of the general formula formula R ₅ H CC = NNR where R is an aromatic-carbocyclic radical, R _{1 is} hydrogen or an alkyl radical, R _{2 is} hydrogen, an alkyl, alkoxy or an optionally substituted by alkyl group or by an acyl, sulfonyl or carbamoyl radical Le A12887 - 30 - 1Q9842M480 Amino group, R, for hydrogen, an Alley 1- or alkoxy group, R. for an alkyl group, R ₅ for the cyano or an optionally substituted carbonamide group and X for an anion and in which the aliphatic, cycloaliphatic and aromatic radicals R, Rj, R ₂ »R ,, R, and R ₅ can have non-ionic substituents with a Hammett constant β-para less than 0.7, characterized in that amines of the formula R-NH ₂ where R is a carbocyclic-aromatic radical, diazotized and with compounds of the general formula C = GH wherein R ^, R ₂ , ET have meaning ', implemented. j and R, - the above mentioned Be 5. Process for the preparation of dyes of general formula R ₂ R, ^C 1 N H' - R Le A12887 1098-42 / 1480 201379. wherein R stands for an aromatic-carbocyclic radical, R ₁ for hydrogen or an alkyl radical, Rp for hydrogen, an alkyl, alkoxy or an amino group optionally substituted by alkyl groups or by an acyl, sulfonyl or carbamoyl radical, R, for hydrogen, an alkyl or alkoxy radical, R. for an alkyl radical, R, - for the cyano or an optionally substituted carbonamide group and X for an anion and in which the aliphatic, cycloaliphatic and aromatic radicals R, R .., Rp, R *, R4 and R, - may have non-ionic substituents with a Hammett constant 0- para less than 0.7, characterized in that amines of the formula R-NH ₂ where R is a carbocyclic-aromatic radical, diazotized and with compounds of the general formula 1 T * in which R-, R ₃ , R », have meanings. Rc and X those given above Le A12887 109842M480 6. Process for the preparation of dyes of general formula C-C = N-N-R wherein R stands for an aromatic-carbocyclic radical, R for hydrogen or an alkyl radical, R ₂ for | Hydrogen, an alkyl, alkoxy or optionally by alkyl groups or by a Acyl, sulfonyl or carbamoyl radical substituted Amino group, R, for hydrogen, an alkyl or alkoxy radical, R. for an alkyl radical, R, - for the Cyano or an optionally substituted carbonamide group, Rg for an alkyl, Aralkyl or cycloalkyl group and X for an anion and in which see the aliphatic, cycloaliphatic and aromatic radicals R, R_, R-, R-, R., Rc and Rg further non-ionic substituents with a Hammett's constant e "para less than 0.7 Λ can, characterized in that compounds of the general formula Le A 12887 - 33 - 1098A2 / U80 ^R 2 _A ^ ^H v? 5 XX = C-N = N-R ^Λ 3 Ν R ₄
in which R, R-,, Rp, R * »R * and R ₁ - have the meaning given above, if appropriate in the presence of a solvent or diluent, if appropriate at elevated temperature with a quaternizing agent, converted into the ammonium compound. 7. Use of the dyes of claims 1, 2 and 3 for dyeing and printing polymers and copolymers of acrylonitrile or as. Dicyanäthylens, of acid-modified polyester and acid-modified Polyamide materials. 8. Use of dyes of claims 1, 2 and 3 for dyeing leather, tanned cotton, writing fluids, of lignin-containing fibers and printing pastes. 9. Materials made from polymers or copolymers of acrylonitrile or as. Dicyanoethylene and acid-modified Polyester or polyamide fibers, dyed or printed with the dyes of claims 1, 2 and 3. Le A 12887 - 34 - 109842/1480